Cellulose process



PatentedJan. -11,, l9

more rnocnss Comm, Del, assignmto nt do Nomonrs a Company, Wil- Del... a corporation Dela Aplication February 1, i985,

This invention relates to the saponlflcation oi esters, more particularly to the seponiflcation of cellulose esters, and still more saponiiication oi the organic esters oi cellulose by an alcoholysis method.

It is nown that cell is rapidly degraded by alkali in the presence of oxygen. I Primarily all of the methods employed in the prior art for completely saponiiying cellulose esters are based 1 on the use oi all either in aqueous, alcoholic,

or pyridine media d thereiore are subject to the danger of deg oi the cellulose during the sapocanon. in; acid hydrolysis r method such as the phosphoric acid method tor regenerating the cellulose from its o 2 .211; c esters degrades the cellulose to such on extent tt it is water-soluble. In addition to these vantages, the methods employed in the prior ert are time consuming in thnt they require several hours to a day, depending upon the method, for complete saponificstion.

This invention has es an object the partial or complete'saponificatlon oi the organic esters of cellulose. A further object is the regeneration of cellulose from its organic esters under essentially non-degrading conditions. A still further object is the reduction of the timeoi saponification as compared with the methods employed in the prior art. Other objects will appear hereinafter.

These objects are accomplished by the following invention wherein n high molecular weight organic acidester of a poly -hydroxy compound is seponiiled by bringing such an ester, tor example, a cellulose ester of on organic acid; in contact with an alcohol in the presence of a metal alcoholate.

The process of the present invention has two principal variations which may be called the homogeneous method and the heterogeneous method. These methods areas follows:

A. Homogeneous method The dry organic ester of cellulose, such as cellulose acetate, benzoete, or acetate henzoate, to be saponifled is dissolved in an anhydrous solvent such as acetone, dioxane, etc., or a mixed solvent. such as toluene-alcohol, etc., which is relatively inert to the metallic alcoholate. The resulting solution is then diluted to the extent of 25400 per cent with an alcohol, such as methyl or ethyl alcohol. To this solution is added with rapid agitation at room temperature a small amount of sodium methylate (1-10 per cent based on the weight of the ester) in the form oi a-m ethyl alrly to the cohol solution. The solution is agitated until gelation occurs which usually requires from one to two minutes. The gel, which is a complex intermediate, is allowed to stand for a few minutes (-60) with intermittent sh in order for the reaction to become complete. The gel is then decomposed by the addition of water which leaves the cellulose in a. semi-gelatinous highly swollen form. The solution is immediately filtered and washed neutral with distilled water. The higher the molecular weight of the substituent acid group in the cellulose, the longer is the time reed for complete saponification. In the saponificetion of the higher esters of cellulose, such es cellulose butyrate, it is advisable to heat the gel intermediateior a few minutes (fill-60) at e temperature of prior to the addition of water.

This method of saponificotion is also applicable to the mixed esters of cellulose, such as cellulose acetate propionate, acetate butyrate, acetate benzoate, etc. The same procedure is emplayed as described above and the gel intermediate is allowed to stand for the same length of time as for the simple ester containing only the highest molecular weight acid radical present in the mixed ester. I

It is extremely diincult to control the degree of saponiilcation by the homogeneous method due to the rapidity of the reaction. However, a partial saponiflcation can be accomplished by the homogeneous method by limiting the quantity of alcohol present in the reaction media. For partial saponiilcation however, the heterogeneous method can be more easily controlled and is simplified by the fact that the ester does' not have to be dissolved in a. solvent prior to saponi- :fication.

By limiting the amount of alcohol, and particularly by the addition of a less rapidly acting alcohol such as propyl or butyl alcohol, partial saponiflcation may be effected in the case of mixed esters such as cellulose acetate propionate, since the acetate is more readily hydrolyzed ofi than is the propionate. This process of partial saponiflcation in a homogeneous system aiiords the possibility of saponiiying the acetate group of! to a large extent, leaving the propionate groups, to a large extent, unaflected. In view of the rapidity of the reaction, extremely good mixing' is required ior'uniiorm results. The bydrolysis or a. cellulose acetate propionate to a product largely consisting'ot propionate, is of course possible also in heterogeneous systems.

B." Heterogeneous method primarily applicable to esters which are in an ex tended physical form, such as powders, films, foils, or yarns. The cellulose ester should be dried prior to saponification so that it does not contain suflicient water to destroy. the alcoholate catalyst. The cellulose ester is immersed in an alcohol solution of an alcoholate (approximately 1 molar) at room temperature until the desired degree of saponification is obtained. The time of saponification depends on the particular cellulose ester being investigated and the physical form of the ester. Acetates are more easilysaponifled than propionates which in turn are more easily saponified than butyrates. Likewise, yarn or fabrics are more easily saponified than films. Furthermore, small changes in the concentration of the sodium methylate solution influence the rate of saponification. In the case of the higher esters, it is also desirable to increase the temperature at which the reaction is carried out to 40-80 C. After the desired degree of saponii'lcation is obtained, the ester is immersed in water which destroys the sodium methylate and the resulting cellulose material is purified by washing with water until neutral.

"The metallic alcoholate such as sodium methylate, ethylate, monosodium glycerinate, etc., may be prepared by slowly adding small clean pieces of the metal, such as sodium, potassium, aluminum, etc., to the dry cool alcohol solution, and allowing the reaction to proceed until all of the metal is dissolved. Extreme care should be taken to exclude moisture'during the preparation of the alcoholate.

The rate of reaction is influenced to a very concatalyst when methyl alcohol is present in the saponification bath. When monosodium glycerinate isemployed as the catalyst and glycerine as the alcohol, little evidence of saponification could be detected after standing ior several hours. Similarly, in the case of octadecyl alcohol. For this reason, lower molecular weight monohydric aliphatic alcohols and particularly methyl alcohol, are preferred. Similarly, sodium methylate is the preferred catalyst altho other alcoholates are satisfactoryin the presence of lower aliphatic Ten grams of dry commercial flake cellulose acetate containing 54.5% of combined acetic acid was dissolved in -l50 cc. of dry dioxane. This solution was diluted with 150 cc. of dry methyl alcohol. The resulting homogeneous solution was then cooled to 12 C. and 18 cc. of a solution of sodium methylate in methyl alcohol added wvith constant shaking. In approximately 3-5 minutes the solution'set to a gel which was: al-

lowed to stand with intermittent shaking in the water bath at 12 C. for 30 minutes. To this gel 150 cc. of ice water was added with constant shaking. The resulting cellulose in a highly swollen form was filtered, washed with water until neutral, and driedat 65 C. Analysis of the cellulose showed that it had been completely deacetylated.

Example 2.( Cellulose proximate-homogeneous method) resulting cellulose was filtered, washed neutral with water, and dried at 105 C. The weight of regenerated cellulose indicated that saponification was complete.

Example 3.-(Cellulose acetate-sodium glycerinate-homogeneous method) Five grams of dry flake cellulose actetate con- I taining 54.5% combined acetic acid was dissolved in 50 cc. of dioxane. This solution was diluted with 50 cc. of dry methyl alcohol. To the resulting homogeneous solution, 50 cc. of a 5% solution of monosodium glycerinate in glycerine was added with constant shaking at room temperature. After approximately minutes of shaking, the solution gelled in the same manner as when sodium methylate is employed as the catalyst. Theresulting .gel was allowed to stand for 30 minutes at room temperature before adding '100 cc. of distilled water. The resulting cellulose was filtered, washed neutral with water and dried at 105 C. Y

Example 4.-(Cellulose buturate-homogeneous method) Eight grams of cellulose butyrate was dissolved in 150 cc. of dioxane and the resulting solution diluted with 150 cc. of dry methyl alcohol. To this solution-40' cc. of a 5% solution of sodium methylate in ethyl alcohol was added at room temperature with constant shaking. Aiterapproximately 10 minutes, the solution gelled. The resulting gel was allowed to stand at room temperature for one hour and then heated for 20 minutes at C. prior to adding 100 cc. of distilled water. The resulting cellulose was filtered,

washed neutral with water, and dried at 65 C.

The weightof the resulting cellulose indicated that saponifica'tlon was complete.

Example 5.(Cellulose acetate poopionate-homogeneous method) hol and ether and drying at 105 geneoae me!) methylate solution was added. a line flocculant illl precipitate formed in the reacdon medium. The resulting solution containing the precipitated cellulose was tated for one hour at room tern .Derature.

To the resulting solution 35 cc. of methyl alcohol and cc. of the 5% um methylate solution were added and the solution heated at 60 C. with agitation for an additional hour. The cellulose was then filtered, M are. with alcohol. water until neutral, then with alcohol and other, and dried at 105 C.

Example 7.-(Celluloce acetate yum-heterogene our method) Small shells: of dry cellulose acetate in m containing 54.5% of combined acetic acid were imniersed at room temperature C.) in a solution containing 150 cc. of methyl alcohol and Blue) and a rayon type dye (Ponne 8w Ellie .X). The rts obtained mm the dyeing tests areas follows:

cose ill ii. Cellulose acetate tum dye e. resum eye 1. Original cellulose tote ya 2. ponifled r d not dye.

3- 'I lil Li 1 min 4. ponifled i minu rayon. 5. Saponified 1o :rfv. darker n viscose rayon. d. V rayon-dyed dart; blue color.

"e series or not-we.

as also carried a with cellulose acetate .iabric in which on one germ of rimgnts an oi the rues w re ublectedtb the sm e Mme? oiZ thelabric was sa In the latter scrim oi tests in which only art oLthe fabric was so.

effects-Were il same depth not e.

, darker than was 3 Emile '8.-=(Cel1ulose acetate film-heterogeneoasmeihod),

Dry cellulose acetate films approximately 0.005" thick containing 54.5% of combined acetic acid were immersed in a solution containing 500 cc. of methyl alcohol and 15, 30, i5,- and 60 cc. of a 5% solution of sodium methylate respectively for 1, 2, 3, and 4 minutes. The resulting films were washed neutral with water and dried at 65 C. The treated films were not analyzed for acetic acid content but their difference in moisture sensitivity, brittleness, and dyeing characteristics indicated that the films had been sa-' ponified to dlflerent degrees.

' The invention is not limited to the hydrolysis of cellulose esters oi organic acids, but may also be applied to high molecular weight glycerides. polyvinyl acetate, and similar high molecular weight esters of organic polyhydric compounds. The rapidity and completeness of the reaction however, depends on the stability of the two types of esters which stability is determined in this case by the ease by which the complex ester is A converted'to the corresponding alcohol with the sumequent formation of the simple ester, such as ethyl acetate. The difference in the stability of the two wters 'may be influencedby a number of factors. such as free energy, negativity, steric hindrance, etc. Inthe application of this reaction to cellulose esters, there is a consider. able difierence in the stability oi the cellulose esters and methyl acetate, and therefore the reaction favors the formation of cellulose and methyl acetate. In the .case of the glycerides, polyvinyl acetate, etc., however, this difference in stabillty'or potential is not nearly so great, therefore the reaction is much slowerland has to be carried out at higher temperatures and under more drastic conditions than with cellulose esters.

The metal employed in thepreparation of alcoholates may be lithium, sodium, potassium, calciuni, megnmium, etc. In i'act, any metal which will form an alcoholate, i. e.. any metal above hydrogen in the electrochemical series may be employed. Thus; aluminum alcoholate is satisfactorily employed as a catalyst. The alkali metal alcoholates however, i. e.. those of sodium, yotassium. and the like, seem to be slightly more effective as catalysts than the slcoholates of the lesser basic metals.

e aliphatic nionohydric lower molecular wemht alcohols are preferred. aromatic alcohols such as a such as glycerol may be employed. Of the allwatic alcohols the rate of reaction decreases as the molecular weight increases in the homologous series, methyl, ethyl, propyl, butyl, etc. In the nolyhydric and aromatic alcohols the reaction is yery slow. In the partial saponificatlon of cellulose mters, it is frequently advantageous to ha e a relatively slow reaction in order to obtain better control. In these. cases. the velocity of the reaction can be controlled to a considerable ticgree of employing an alcohol in the range nr nyl. butyl. etc.

The alcohol employed in the preparation of. the alcoholate ls-not limited to aliphatic -m0no-, hydric alcohols'for polyhydric alcohols may be employed as well as aromatic alcohols, such as .benzyl alcoholl' The alcoholates cf the aromatic and polyhydric alcoholsseem to be just as eflectire as the .alcobclate oi the aliphatic mono- Wdric alcohol when a low molecular weight all or alcohol, and polyhydric alcohols phatic alcohoL-such as methyl or ethyl alcohol is employed as the alcohol diluent in the reaction medium.

The conditions under which the reaction is carried out may be varied within wide limits. The temperature employed may be varied from the freezing point to the boiling point of the solvent or diluent employed in the reaction. In the homogeneous-reaction, any solvent may be employed which does not react with the' metal 'alcoholate catalyst such as ketones. stable chlorinated hydrocarbons, hydrocarbons both allphatic and aromatic, others. etc. The proportion of alcohol employed as a diluent or reaction medium may be varied from molar quantities to several hundred per cent excess. when larse excesses oi. alcohol are employed, the alcohol should be relatively free from water in order to prevent destruction of the catalyst. The concentration of catalyst (alcoholate) may be varled within wide limits from a mere trace to several per cent based on the weight of the ester. since the reaction is a chain reaction, a mere trace (om-0.1%) of catalyst on the weight of the ester is suillcient. The smaller the amount of catalyst employed, however, the slower isthe rate of reaction. In the preferred procedure for the complete saponiilcation oi cellulose ester. in which sodium methylatc is employed as the catalyst andmethyl alcohol as diluent or reaction medium. therein is can ried out between 20 and 80 C. 1 The concentration of catalyst ordinarily employed is from 5 to based on the weight oi the wes or even to or 50% with higher fatty esters or cellulose and/or higher alcoholate catalysts such as sodium glycerinate, or from 0.05% to 0.1% based on the weight of the dium.

in the heterogeneous ester may be steeped in the capo passed therethrough in a oontin saponiflcation liquid may Drinted, etc.-on the cellulose fabric, etc. and later washed time.

While the process is generally applicable to cellulose esters of organic acids. it does not seem to be applicable to the inc esters of celluiose.'attempts to regenerate ceilul from cellulose nitrate (denitration) being .i'

The most probable explanstionior' the m ,nism of this invention is as follows:

on com a. R-O C- CKk- BOH+CHIQOOOHl The process oi the present invention is of considerable fundamental importance' in oifering a method for regenerating the cellulose from cellulose esters under extremely mild conditions ehalso be applied to the modification of the physical properties of cellulose ester time and foils. Thus. the dyeing characteristics. intangible properties such as luster. feel. weaving characteristiu, etc.. and heat resistance of cellulose esters maybealteredbytheprocess ofthe'present invention. The process of the present inventionpermits the attainment of cross-dyeingeitests on fabrics prepared from one cellulose ester material wherein a portion of the fabric in the desired design is partially or completely saponifled prior to dyeing. This cross-dyeing process has not been feasible in the past with fabrics made from but one ester due to the slow rate of saponiiications oi the processes described in the prior art. The physical properties of ester fabrics are greatly modified by the degree of saponiilcation. The luster of cellulose acetote fabric seems to be enhanced by a slight saponiiication but as the degree of saponiiication increases the luster to some extent decreases.

A subject which is of considerable commercial interest is the improvement in heating rce oi cellulose acetate fabrics. This has been a0- compli'shed in the past by partial saponlflcation.

The present invention is of considerable advantage over the prior art method in carrying out the partial sapcnliications because of the dec in time involved in the treaent.

The process oi the present vention is 2'; to those of the prior in that it is a pie operate, is lws c consuming, and is l P. in action. The greater simplicity of due to the fact that the otion-may be carried out at a lower tempera, the reagent reqd is not so in: and the saponiiied product is "we. to purify apes iron: excess alkali w oi the aller enact of caustic agents present. The extreme. rapidity at which the wpocation are cheated by the process oi the present invei'ition makes it particularly advantageous over it of the prior art;

rapidi with the simplicity oi otion v is: most this as in w 1' sheets with cellul acetate. e mild conditions imder wmch the sapoation oi the present invention is eed out represents one of the ost important advam cs oi the In the regeneration of cellulose from ccllulose esters, it is o deslrehie irom the point of view oi quality oil the resulting cellul not dege the cellulose dull ing saponiflcation. The cellulose in cellulose acetate is not degraded by the saponification procedure oi the present invention, whereas the methods of the prior art such as aqueous mponifications are well we to be degrading in action due'to alkaline 'oxition oi the cellulose. ii.

plete saponiflcatlon of esters icy the process oi the pt invention so that the resuiting cellulose y he more completely recovered from the reaction media.

The above description and examples are intended to he illustrative only. Any modification oi or variation therefrom which conforms-to the spirit of the invention is intended to be included further attent of some imnce is hydrlc alcohol of 1-2 carbon atoms in the pres- 7g holate.

3. Process for the saponiilcation of cellulose acetate, which comprises bringing said ester in contact with an aliphatic monohydric alcohol of 1-2 carbon atoms in the presence of irom 0.01 to 10% of a metal alcoholate.

4. Process for the saponiflcation of cellulose acetate, which comprises bringing said ester in contact with an aliphatic monohydric alcohol of 1-2 carbon atoms in'the presence of from 0.01 to 10% of an alkali metal alcoholate.

5. Process for the saponification of a cellulose ester of an organic acid, which comprises bringing said ester dissolved in an inert solvent in contact with an aliphatic monohydric alcohol of 1-2 carbon atoms in the presence of from 0.01 to 10% of a metal alcoholate.

6. Process for the saponiflcation of a cellulose ester of an organic acid, which comprises bringing said ester dissolved in an inert solvent in contact with an aliphatic monohydric alcohol oi 1-2 carbon atoms in the presence of from 0.01 to 10% of an alkali metal. alcoholate.

7. Process for the saponiflcation of cellulose acetate, which comprises bringing said ester dissolved in an inert solvent in contact with an aliphatlc monohydric alcohol of 1-2 carbon atoms in the presence oi. from 0.01 to 10% of a metal alcoholate.

8. Process for the saponiflcation of cellulose acetate, which comprises bringing said ester dissolved in an inert solvent in contact with an aliphatic monohydric alcohol oil-2 carbon atoms in the presence of from 0.01 to 10% of an alkali metal alcoholate.

9. Process for the saponiflcation of a cellulose ester of an organicacid, which comprises bringing said ester in the solid state in contact with an aliphatic monohydric alcohol of 1-2 carbon atoms in the presence of from 0.01 to 10% of a metal alcoholate.

10. Process for the saponiflcation of a cellulose ester of an organicacid, which comprises bringing said ester in the solid state in contact with an aliphatic monohydric alcohol of 1-2 carbon atoms in the presence of from 0.01 to 10% of an al metal alcoholate.

1 l L- acetate, whicn bringing said ester in the solid state in contact with an aliphatic monohydric alcohol of 1-2 carbon atoms in the presence of from 0.01 to 10% of a metal alcoholate.

12. Pr for the saponincation of cellulose acetate, which comprises bringing said ester in the solidstate in contact with an aliphatic monoliydrio alcohol of 1--2 carbon in the 9&

as for the sapotion of celluloseence of from 0.01 to 10% of an alkali metal alco= holate.

13. Process for the saponification of cellulose acetate, which comprises bringing the same in contact with methanol in the presence oi 0.05 to 0.1% of sodium methylate based on the weight of the cellulose at a temperature between 20 and 80 C.

14. The process which comprises mixing cellulose acetate with an alcohol 01 the group consisting of methyl alcohol and ethyl alcohol and an alkali metal alcoholate of the group consisting of from 0.01 to 10% of alkali metal methylates and alkali metal ethylates, maintaining the mixture until saponiflcation of the cellulose acetate has taken place and then isolating the saponifled cellulosic body from the saponifying mixture.

15. The process which comprises mixing a cellulose ester with an alcohol of the group conslsting of methyl alcohol and ethyl alcohol and from 0.01 to 10% of an alkali metal alcoholate oi the group consisting of alkali metal methylates and alkali metal ethylates, maintaining the mixture until saponiflcation of the cellulose ester has taken place and then isolating the saponifled celluiosic body from the saponiiying mixture.

16. The process oi claim 14 in which the alcohol is ethyl alcohol.

17. The process which comprises dissolving 10 grams of cellulose acetate containing about 54.5% combined acetic acid in 150 cc. dioxane, cooling to 12 0,, adding 18 cc. of sodium methylate in methyl alcohol solution with agitation, maintaining the mixture at about 12 C. for 30 minutes and isolating the saponifled' cellulose.

18. The process lor the saponification of a cellulose ester of an organic acid, which comprises bringing said ester in contact with an aliphatic monohydric alcohol of one to two carbon atoms in the presence of from 0.01 to of a metal alcoholate, maintaining the mixture under reaction conditions until the saponification of the cellulose ester has taken place to such an extent that there is a distinct change in its dyeing characteristics. I

19. The process for the saponiflcation of cellulose acetate which comprises bringing said ester in contact with an alcohol 0! the group consisting of methyl and ethyl alcohol and from 0.01 to 10% 01 an alkli metal alcoholate,'and continuing the reaction until the cellulose acetate has been saponified to such an extent that it is readily receptive to a viscose rayon-type dye.

nouns F. CONAWAY. 

